6-(2-chloro-6-fluoro-phenyl)-triazolopyrimidines

ABSTRACT

6-(2-Chloro-6-fluoro-phenyl)-triazolopyrimidines of formula (I), in which R 1  and R 2  independently denote hydrogen or alkyl, alkenyl, alkynyl, alkadienyl, or haloalkyl, cycloalkyl, bicycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or where R 1  and R 2  radicals may be unsubstituted or partially or fully halogenated or may be substituted as defined in the description. R 1  and R 2  together with the interjacent nitrogen atom represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted; X is cyano, alkoxy, haloalkoxy or alkenyloxy; processes for their preparation, compositions containing them and to their use for combating phytopathogenic fungi

The invention relates to6-(2-chloro-6-fluoro-phenyl)-triazolopyrimidines of formula I

in which

R¹ and R² independently denote hydrogen or

-   -   C₁–C₁₀-alkyl, C₂–C₁₀-alkenyl, C₂–C₁₀-alkynyl, C₄–C₁₀-alkadienyl,        or C₁–C₁₀-haloalkyl,    -   C₃–C₈-cycloalkyl, C₅–C₁₀-bicycloalkyl, phenyl, naphthyl, or 5-        or 6-membered heterocyclyl, containing one to four nitrogen        atoms or one to three nitrogen atoms and one sulfur or oxygen        atom, or    -   5- or 6-membered heteroaryl, containing one to four nitrogen        atoms or one to three nitrogen atoms and one sulfur or oxygen        atom, or    -   where R¹ and R² radicals may be unsubstituted or partially or        fully halogenated or may carry one to three groups R^(a),    -   R^(a) is halogen, cyano, nitro, hydroxyl, C₁–C₆-alkyl,        C₁–C₆-haloalkyl, C₃–C₆-cycloalkyl, C₁–C₆-alkoxy,        C₁–C₆-haloalkoxy, C₁–C₆-alkylthio, C₁–C₆-alkylamino,        di-C₁–C₆-alkylamino, C₂–C₆-alkenyl, C₂–C₆-alkenyloxy,        C₂–C₆-alkynyl, C₃–C₆-alkynyloxy and C₁–C₄-alkylenedioxy, which        may be halogenated; or

R¹ and R² together with the interjacent nitrogen atom represent a 5- or6-membered heterocyclic ring, containing one to four nitrogen atoms orone to three nitrogen atoms and one sulfur or oxygen atom, which may besubstituted by one to three R^(a) radicals;

X is cyano, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy or C₃–C₈-alkenyloxy.

Moreover, the invention relates to processes for their preparation,compositions containing them and to their use for combatingphytopathogenic fungi.

EP-A 071 792 discloses 6-phenyl-7-amino-triazolopyrimidines where the5-position is substituted by hydrogen or alkyl or aryl groups.

EP-A 550 113 relates to 5-H- and5-halogen-6-phenyl-7-amino-tri-azolopyrimidines where the 7-amino groupis further substituted.

WO-A 98/46607 discloses triazolopyrimidines, which are substituted inthe 6-position by a 2,4,6-trifluorophenyl group.

U.S. Pat. No. 5,994,360 discloses triazolopyrimidines, which aresubstituted in the 5-position by alkyl groups.

The compounds disclosed in the documents discussed above are said to beactive against various phytopathogenic fungi.

It is an object of the present invention to provide compounds havingimproved fungicidal activity.

We have found that this object is achieved by the compounds defined atthe outset. Furthermore, we have found processes for their preparation,compositions comprising them and methods for controlling phytopathogenicfungi using the compounds I.

The compounds of the formula I differ from the compounds known from theabovementioned art in the combination of the 2-chloro-6-fluoro-phenylgroup and a specific substitution in 5-position of thetriazolopyrimidine system.

A 4- to 6-membered heterocyclic group may be any heterocyclic group with4 to 6 ring atoms, interrupted by one or more heteroatoms selected fromsulfur, nitrogen, and oxygen, preferably oxygen. A halogen atom suitabledenotes a fluorine, chlorine or bromine atom.

The present invention further provides a process for the preparation ofcompounds of formula I as defined above which comprises treating a5-halogen compound of formula II

in which Y is halogen with a compound of formula III, which is,dependent from the value of X to be introduced to yield formula Icompounds, an anorganic cyano salt, an alkoxylate, haloalkoxylate or analkenyloxylate, respectively, preferably in the presence of a a solvent.The cation M in formula III has minor influence; for practical andeconomical reasons usually ammonium-, tetraalkylammonium- oralkalimetal- and earth metal salts are preferred.

Suitable solvents include ethers, such as dioxane, diethyl ether and,especially, tetrahydrofuran, halogenated hydrocarbons such asdichloromethane and aromatic hydrocarbons, for example toluene.

The reaction is suitably carried out at a temperature in the range from0 to 120° C., the preferred reaction temperature being from 10 to 40° C.

It is also preferred that the reaction is carried out in the presence ofa base. Suitable bases include tertiary amines, such as triethylamine,and inorganic bases, such as potassium carbonate or sodium carbonate.Alternatively, an excess of the compound of formula III may serve as abase.

The reaction mixtures are worked up in a customary manner, for exampleby mixing with water, phase separation and, if required, chromatographicpurification of the crude products. Some of the end products areobtained in the form of colorless or slightly brownish, viscous oils,which are purified or freed from volatile components under reducedpressure and at moderately elevated temperatures. If the end productsare obtained as solids, purification can also be carried out byrecrystallization or digestion.

Compounds of formula II are known in the art and can be obtained bysynthesis routes disclosed in EP-A 550 113 and WO-A 98/46608.

If individual compounds I are not obtainable by the routes describedabove, they can be prepared by derivatization of other compounds I.

In the symbol definitions given in the formulae above, collective termswere used which generally represent the following substituents:

-   -   halogen: fluorine, chlorine, bromine and iodine;    -   C₁–C₁₀-alkyl and the alkyl moieties of C₁–C₁₀-haloalkyl:        saturated, straight-chain or branched hydrocarbon radicals        having 1 to 10, especially 1 to 6 carbon atoms, for example        C₁–C₄-alkyl as mentioned above or pentyl, 1-methylbutyl,        2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl,        1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,        1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,        1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,        2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,        1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,        1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and        1-ethyl-2-methylpropyl;    -   C₁–C₆-haloalkyl and the haloalkyl moieties of C₁–C₆-haloalkoxy:        straight-chain or branched alkyl groups having 1 to 6,        preferably 1 to 4 carbon atoms (as mentioned above), where the        hydrogen atoms in these groups may be partially or fully        replaced by halogen atoms as mentioned above, for example        C₁–C₂-haloalkyl, such as chloromethyl, bromomethyl,        dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,        trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl,        chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl,        1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,        2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,        2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,        2,2,2-trichloroethyl and pentafluoroethyl;    -   C₃–C₁₀-alkenyl: unsaturated, straight-chain or branched        hydrocarbon radicals having 3 to 10, especially 3 to 6 carbon        atoms and a double bond in any position, for example 1-propenyl,        2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,        1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl        and 2-methyl-2-propenyl;    -   C₂–C₁₀-alkynyl: straight-chain or branched hydrocarbon radicals        having 2 to 10, especially 2 to 4 carbon atoms and a triple bond        in any position, for example ethynyl, 1-propynyl, 2-propynyl,        1-butynyl, 2-butynyl, 3-butynyl and 1-methyl-2-propynyl;    -   In general terms, the term cycloalkyl, as used herein with        respect to a radical or moiety refers to a cycloalkyl group        having 3 to 8 carbon atoms, preferably 5 to 7 carbon atoms.    -   In general terms, the term bicycloalkyl, as used herein with        respect to a radical or moiety refers to a bicycloalkyl group        having 5 to 10 carbon atoms, preferably 6 to 9 carbon atoms, in        particular bicycloheptyl being optionally substituted by one or        more halogen atoms, nitro, cyano, alkyl, preferably C₁₋₆ alkyl,        alkoxy, preferably C₁₋₆ alkoxy.    -   5-membered heteroaryl, containing one to four nitrogen atoms or        one to three nitrogen atoms and one sulfur or oxygen atom:        5-membered heteroaryl groups which, in addition to carbon atoms,        may contain one to four nitrogen atoms or one to three nitrogen        atoms and one sulfur or oxygen atom as ring members, for example        2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl,        3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,        4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl,        5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl,        4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,        1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,        1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,        1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl        and 1,3,4-triazol-2-yl;    -   6-membered heteroaryl, containing one to four nitrogen atoms:        6-membered heteroaryl groups which, in addition to carbon atoms,        may contain one to three or one to four nitrogen atoms as ring        members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,        3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl,        5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and        1,2,4-triazin-3-yl.

With respect to their intended use, preference is given totriazolopyrimidines of the formula I having the following substituents,where the preference is valid in each case on its own or in combination:

The particularly preferred embodiments of the intermediates with respectto the variables correspond to those of the radicals X, R¹ and R² offormula I.

A preferred alkyl moiety is an ethyl or especially a methyl group.

A preferred haloalkyl moiety is the 2,2,2-trifluoroethyl or1,1,1-trifluoroprop-2-yl group;

A preferred alkenyl moiety is allyl or especially a 2-methylallyl group.

A preferred cycloalkyl moiety is cyclopentyl being optionallysubstituted by one or more halogen atoms, nitro, cyano, alkyl,preferably C₁–C₆ alkyl, alkoxy, preferably C₁–C₆ alkoxy.

A preferred heteroaryl moiety is pyridyl, pyrimidyl, pyrazolyl orthienyl.

Preference is given to compounds of formula I in which any alkyl orhaloalkyl part of the groups R¹ or R², which may be straight chained orbranched, contains up to 10 carbon atoms, preferably 1 to 9 carbonatoms, more preferably 2 to 6 carbon atoms, any alkenyl or alkynyl partof the substituents R¹ or R² contains up to 10 carbon atoms, preferably2 to 9 carbon atoms, more preferably 3 to 6 carbon atoms, any cycloalkylpart of the substituents R¹ or R² contains from 3 to 10 carbon atoms,preferably from 3 to 8 carbon atoms, more preferably from 3 to 6 carbonatoms, and any: bicycloalkyl part of the substituents R¹ or R² containsfrom 5 to 9 carbon atoms, preferably from 7 to 9 carbon atoms. Anyalkyl, alkenyl or alkynyl group may be linear or branched.

Likewise, preference is given to compounds of formula I wherein R¹ isnot hydrogen.

Compounds of formula I are preferred in which R¹ represents astraight-chained or branched C₁–C₁₀-alkyl, in particular a branchedC₃–C₁₀-alkyl group, a C₃–C₈-cycloalkyl, a C₅–C₉-bicycloalkyl, aC₃–C₈-cycloalkyl-C₁–C₆-alkyl, C₁—C₁₀-alkoxy-C₁–C₆-alkyl, aC₁–C₁₀-haloalkyl or a phenyl group being optionally substituted by oneto three halogen atoms or C₁–C₁₀-alkyl or C₁–C₁₀-alkoxy groups.

Particular preference is given to compounds I in which R² represents ahydrogen atom, a C₁–C₁₀-alkyl or a C₁–C₁₀-haloalkyl group, in particulara hydrogen atom.

Besides, particular preference is given to compounds I in which R² ishydrogen.

Moreover, particular preference is given to compounds I in which R² ismethyl.

Furthermore, particular preference is given to compounds I in which R²is ethyl.

If R¹ denotes a C₁–C₁₀-haloalkyl group, preferably a polyfluorinatedalkyl group, in particular a 2,2,2-trifluoroethyl, a2-(1,1,1-trifluoropropyl) or a 2-(1,1,1-trifluorobutyl) group, R²preferably represents a hydrogen atom.

If R¹ denotes an optionally substituted C₃–C₈-cycloalkyl group,preferably a cyclopentyl or cyclohexyl group, R² preferably represents ahydrogen atom or C₁–C₆-alkyl group.

Moreover, particular preference is given to compounds I in which R¹ andR² together with the interjacent nitrogen atom form an optionallysubstituted heterocyclic ring, preferably an optionally substitutedC₃–C₇-heterocyclic ring, in particular a pyrrolidine, piperidine,tetrahydropyridine, in particular 1,2,3,6-tetrahydropyridine or azepanering which is optionally substituted by one or more C₁–C₁₀-alkyl groups.

Included in the scope of the present invention are (R) and (S) isomersof compounds of general formula I having a chiral center and theracemates thereof, and salts, N-oxides and acid addition compounds.

With respect to their use, particular preference is given to thecompounds I compiled in the tables below. The groups mentioned in thetables for a substituent are furthermore for their part, independentlyof the combination in which they are mentioned, a particularly preferredembodiment of the respective substituents.

Table 1

Compounds of the formula I, in which X is cyano and R¹ and R² correspondto one row in Table A

Table 2

Compounds of the formula I, in which X is methoxy and R¹ and R²correspond to one row in Table A

Table 3

Compounds of the formula I, in which X is ethoxy and R¹ and R²correspond to one row in Table A

Table 4

Compounds of the formula I, in which X is n-propoxy and R¹ and R²correspond to one row in Table A

Table 5

Compounds of the formula I, in which X is iso-propoxy and R¹ and R²correspond to one row in Table A

Table 6

Compounds of the formula 1, in which X is allyloxy and R¹ and R²correspond to one row in Table A

Table 7

Compounds of the formula I, in which X is 3-methylallyloxy and R¹ and R²correspond to one row in Table A

Table 8

Compounds of the formula I, in which X is fluoromethoxy and R¹ and R²correspond to one row in Table A

Table 9

Compounds of the formula I, in which X is difluoromethoxy and R¹ and R²correspond to one row in Table A

Table 10

Compounds of the formula I, in which X is trifluoromethoxy and R¹ and R²correspond to one row in Table A

TABLE A I

No. R¹ R² A-1 CH₂CH₃ H A-2 CH₂CH₃ CH₃ A-3 CH₂CH₃ CH₂CH₃ A-4 CH₂CF₃ H A-5CH₂CF₃ CH₃ A-6 CH₂CF₃ CH₂CH₃ A-7 CH₂CCl₃ H A-8 CH₂CCl₃ CH₃ A-9 CH₂CCl₃CH₂CH₃ A-10 CH₂CH₂CH₃ H A-11 CH₂CH₂CH₃ CH₃ A-12 CH₂CH₂CH₃ CH₂CH₃ A-13CH₂CH₂CH₃ CH₂CH₂CH₃ A-14 CH(CH₃)₂ H A-15 CH(CH₃)₂ CH₃ A-16 CH(CH₃)₂CH₂CH₃ A-17 (±) CH(CH₃)—CH₂CH₃ H A-18 (±) CH(CH₃)—CH₂CH₃ CH₃ A-19 (±)CH(CH₃)—CH₂CH₃ CH₂CH₃ A-20 (R) CH(CH₃)—CH₂CH₃ H A-21 (R) CH(CH₃)—CH₂CH₃CH₃ A-22 (R) CH(CH₃)—CH₂CH₃ CH₂CH₃ A-23 (S) CH(CH₃)—CH₂CH₃ H A-24 (S)CH(CH₃)—CH₂CH₃ CH₃ A-25 (S) CH(CH₃)—CH₂CH₃ CH₂CH₃ A-26 (±)CH(CH₃)—CH(CH₃)₂ H A-27 (±) CH(CH₃)—CH(CH₃)₂ CH₃ A-28 (±)CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-29 (R) CH(CH₃)—CH(CH₃)₂ H A-30 (R)CH(CH₃)—CH(CH₃)₂ CH₃ A-31 (R) CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-32 (S)CH(CH₃)—CH(CH₃)₂ H A-33 (S) CH(CH₃)—CH(CH₃)₂ CH₃ A-34 (S)CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-35 (±) CH(CH₃)—C(CH₃)₃ H A-36 (±)CH(CH₃)—C(CH₃)₃ CH₃ A-37 (±) CH(CH₃)—C(CH₃)₃ CH₂CH₃ A-38 (R)CH(CH₃)—C(CH₃)₃ H A-39 (R) CH(CH₃)—C(CH₃)₃ CH₃ A-40 (R) CH(CH₃)—C(CH₃)₃CH₂CH₃ A-41 (S) CH(CH₃)—C(CH₃)₃ H A-42 (S) CH(CH₃)—C(CH₃)₃ CH₃ A-43 (S)CH(CH₃)—C(CH₃)₃ CH₂CH₃ A-44 (±) CH(CH₃)—CF₃ H A-45 (±) CH(CH₃)—CF₃ CH₃A-46 (±) CH(CH₃)—CF₃ CH₂CH₃ A-47 (R) CH(CH₃)—CF₃ H A-48 (R) CH(CH₃)—CF₃CH₃ A-49 (R) CH(CH₃)—CF₃ CH₂CH₃ A-50 (S) CH(CH₃)—CF₃ H A-51 (S)CH(CH₃)—CF₃ CH₃ A-52 (S) CH(CH₃)—CF₃ CH₂CH₃ A-53 (±) CH(CH₃)—CCl₃ H A-54(±) CH(CH₃)—CCl₃ CH₃ A-55 (±) CH(CH₃)—CCl₃ CH₂CH₃ A-56 (R) CH(CH₃)—CCl₃H A-57 (R) CH(CH₃)—CCl₃ CH₃ A-58 (R) CH(CH₃)—CCl₃ CH₂CH₃ A-59 (S)CH(CH₃)—CCl₃ H A-60 (S) CH(CH₃)—CCl₃ CH₃ A-61 (S) CH(CH₃)—CCl₃ CH₂CH₃A-62 CH₂C(CH₃)═CH₂ H A-63 CH₂C(CH₃)═CH₂ CH₃ A-64 CH₂C(CH₃)═CH₂ CH₂CH₃A-65 cyclopentyl H A-66 cyclopentyl CH₃ A-67 cyclopentyl CH₂CH₃ A-68—(CH₂)₂CH(CH₃)(CH₂)₂—

The compounds I are suitable as fungicides. They have outstandingactivity against a broad spectrum of phytopathogenic fungi, inparticular from the classes of the Ascomycetes, Deuteromycetes,Phycomycetes and Basidiomiycetes. Some of them act systemically, andthey can be employed in crop protection as foliar- and soil-actingfungicides.

They are especially important for controlling a large number of fungi ona variety of crop plants such as wheat, rye, barley, oats, rice, maize,grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruitspecies, ornamentals and vegetables such as cucumbers, beans, tomatoes,potatoes and cucurbits, and on the seeds of these plants.

Specifically, they are suitable for controlling the following plantdiseases:

-   Alternaria species on vegetables and fruit,-   Botrytis cinerea (gray mold) on strawberries, vegetables,    ornamentals and grapevines,-   Cercospora arachidicola on peanuts,-   Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,-   Blumeria graminis (powdery mildew) on cereals,-   Fusarium and Verticillium species on various plants,-   Helminthosporium species on cereals,-   Mycosphaerella species on bananas and peanuts,-   Phytophthora infestans on potatoes and tomatoes,-   Plasmopara viticola on grapevines,-   Podosphaera leucotricha on apples,-   Pseudocercosporella herpotrichoides on wheat and barley,-   Pseudoperonospora species on hops and cucumbers,-   Puccinia species on cereals,-   Pyricularia oryzae on rice,-   Rhizoctonia species on cotton, rice and lawns,-   Septoria species in cereals,-   Uncinula necator on grapevines,-   Ustilago species on cereals and sugar cane, and-   Venturia species (scab) on apples and pears.

Moreover, the compounds I are suitable for controlling harmful fungisuch as Paecilomyces variotii in the protection of materials (e.g. wood,paper, paint dispersions, fibers and tissues) and in the protection ofstored products.

The compounds I are applied by treating the fungi, or the plants, seeds,materials or the soil to be protected against fungal infection, with afungicidally active amount of the active ingredients. Application can beeffected both before and after infection of the materials, plants orseeds by the fungi.

In general, the fungicidal compositions comprise from 0.1 to 95,preferably 0.5 to 90, % by weight of active ingredient.

When used in crop protection, the rates of application are from 0.01 to2.0 kg of active ingredient per ha, depending on the nature of theeffect desired.

In the treatment of seed, amounts of active ingredient of from 0.001 to0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram ofseed.

When used in the protection of materials or stored products, the rate ofapplication of active ingredient depends on the nature of the field ofapplication and on the effect desired. Rates of applicationconventionally used in the protection of materials are, for example,from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredientper cubic meter of material treated.

The compounds I can be converted into the customary formulations, e.g.solutions, emulsions, suspensions, dusts, powders, pastes and granules.The use form depends on the particular purpose; in any case, it shouldguarantee a fine and uniform distribution of the compound according tothe invention.

The formulations are prepared in a known manner, e.g. by extending theactive ingredient with solvents and/or carriers, if desired usingemulsifiers and dispersants, it also being possible to use other organicsolventsas auxiliary solvents if water is used as the diluent.Auxiliaries which are suitable are essentially: solvents such asaromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes),paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol,butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine,dimethylformamide) and water; carriers such asground natural minerals(e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g.highly-disperse silica, silicates); emulsifiers such as non-ionic andanionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants such aslignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids andtheir alkali metal and alkaline earth metal salts, salts of sulfatedfatty alcohol glycol ether, condensates of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensates of naphthalene orof napthalenesulfonic acid with phenol or formaldehyde, polyoxyethyleneoctylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite wasteliquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,strongly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone and water.

Powders, materials for scattering and dusts can be prepared by mixing orconcomitantly grinding the active substances with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active ingredients to solidcarriers. Examples of solid carriers are mineral earths, such as silicagels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground synthetic materials, fertilizers, e.g.ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, andproducts of vegetable origin, such as cereal meal, tree bark meal, woodmeal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise of from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active ingredient. Theactive ingredients are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are exemplary formulations:

-   I. 5 parts by weight of a compound according to the invention are    mixed intimately with 95 parts by weight of finely divided kaolin.    This gives a dust which comprises 5% by weight of the active    ingredient.-   II. 30 parts by weight of a compound according to the invention are    mixed intimately with a mixture of 92 parts by weight of pulverulent    silica gel and 8 parts by weight of paraffin oil which had been    sprayed onto the surface of this silica gel. This gives a    formulation of the active ingredient with good adhesion properties    (comprises 23% by weight of active ingredient).-   III. 10 parts by weight of a compound according to the invention are    dissolved in a mixture composed of 90 parts by weight of xylene, 6    parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1    mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium    dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40    mol of ethylene oxide and 1 mol of castor oil (comprises 9% by    weight of active ingredient).-   IV. 20 parts by weight of a compound according to the invention are    dissolved in a mixture composed of 60 parts by weight of    cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight    of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol    and 5 parts by weight of the adduct of 40 mol of ethylene oxide and    1 mol of castor oil (comprises 16% by weight of active ingredient).-   V. 80 parts by weight of a compound according to the invention are    mixed thoroughly with 3 parts by weight of sodium    diisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the    sodium salt of a lignosulfonic acid from a sulfite waste liquor and    7 parts by weight of pulverulent silica gel, and the mixture is    ground in a hammer mill (comprises 80% by weight of active    ingredient).-   VI. 90 parts by weight of a compound according to the invention are    mixed with 10 parts by weight of N-methyl-α-pyrrolidone, which gives    a solution which is suitable for use in the form of microdrops    (comprises 90% by weight of active ingredient).-   VII. 20 parts by weight of a compound according to the invention are    dissolved in a mixture composed of 40 parts by weight of    cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight    of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol    and 10 parts by weight of the adduct of 40 mol of ethylene oxide and    1 mol of castor oil. Pouring the solution into 100,000 parts by    weight of water and finely distributing it therein gives an aqueous    dispersion which comprises 0.02% by weight of the active ingredient.-   VIII. 20 parts by weight of a compound according to the invention    are mixed thoroughly with 3 parts by weight of sodium    diisobutylnaphthalene-a-sulfonate, 17 parts by weight of the sodium    salt of a lignosulfonic acid from a sulfite waste liquor and 60    parts by weight of pulverulent silica gel, and the mixture is ground    in a hammer mill. Finely distributing the mixture in 20,000 parts by    weight of water gives a spray mixture which comprises 0.1% by weight    of the active ingredient.

The active ingredients can be used as such, in the form of theirformulations or the use forms prepared therefrom, e.g. in the form ofdirectly sprayable solutions, powders, suspensions or dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading, orgranules, by means of spraying, atomizing, dusting, scattering orpouring. The use forms depend entirely on the intended purposes; in anycase, this is intended to guarantee the finest possible distribution ofthe active ingredients according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances as suchor dissolved in an oil or solvent, can be homogenized in water by meansof wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use products can bevaried within substantial ranges. In general, they are from 0.0001 to10%, preferably from 0.01 to 1%.

The active ingredients may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active ingredient, or even the activeingredient without additives.

Various types of oils, herbicides., fungicides, other pesticides, orbactericides may be added to the active ingredients, if appropriate alsoonly immediately prior to use (tank mix). These agents can be admixedwith the agents according to the invention in a weight ratio of 1:10 to10:1.

In the use form as fungicides, the compositions according to theinvention can also be present together with other active ingredients,e.g. with herbicides, insecticides, growth regulators, fungicides orelse with fertilizers. Mixing the compounds I or the compositionscomprising them in the use form as fungicides with other fungicidesfrequently results in a broader fungicidal spectrum of action.

The following list of fungicides, together with which the compoundsaccording to the invention can be used, is intended to illustrate thepossible combinations, but not to impose any limitation:

-   -   sulfur, dithiocarbamates and their derivatives, such as        iron (III) dime thyldithiocarbamate, zinc        dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate,        manganese ethylenebisdithiocarbamate, manganese zinc        ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide,        ammonia complex of zinc (N,N-ethylenebisdithiocarbamate),        ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc        (N,N′-propylenebisdithiocarbamate),        N,N′-polypropylenebis(thiocarbamoyl)disulfide;    -   nitro derivatives, such as dinitro(1-methylheptyl)phenyl        crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,        2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl        5-nitro-isophthalate;    -   heterocyclic substances, such as 2-heptadecyl-2-imidazoline        acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine,        O,O-diethyl phthalimidophosphonothioate,        5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,        2,3-dicyano-1,4-dithioanthraquinone,        2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl        1-(butylcarbamoyl)-2-benzimidazolecarbamate,        2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole,        2-(4-thiazolyl)benzimidazole,        N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,        N-trichloromethylthiotetrahydrophthalimide,        N-trichloromethylthiophthalimide,        N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfo-diamide,        5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,        2-thiocyanatomethylthiobenzothiazole,        1,4-dichloro-2,5-dimethoxybenzene,        4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,        pyridine-2-thiol 1-oxide, 8-hydroxyquinoline or its copper salt,        2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,        2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,        2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,        2-methylfuran-3-carboxanilide,        2,5-dimethylfuran-3-carboxanilide,        2,4,5-trimethylfuran-3-carboxanilide,        N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,        N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,        2-methylbenzanilide, 2-iodobenzanilide,        N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,        piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,        1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane;        2,6-dimethyl-N-tridecylmorpholine or its salts,        2,6-dimethyl-N-cyclododecylmorpholine or its salts,        N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethyl-morpholine,        N-[3-(p-tert-butylphenyl)-2-methylpropyl]-piperidine,        1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,        1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,        N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea,        1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,        1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,        (2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)-oxiran-2-ylmethyl]-1H-1,2,4-triazole,        α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,        5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,        bis(p-chlorophenyl)-3-pyridinemethanol,        1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,        1,2-bis(3-methoxycarbonyl-2-thioureido)benzene, strobilurines        such as azoxystrobin, kresoxim methyl,        methyl-E-methoxyimino-[α-(2-phenoxyphenyl)]-acetamide, methyl        E-methoxyimino-[α-(2,5-dimethylphenoxyl)-o-tolyl]acetamide,        picoxystrobin, pyraclostrobin, trifloxystrobin,        anilinopyrimidines such as        N-(4,6-dimethylpyrimidin-2-yl)aniline,        N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]-aniline,        N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline, phenylpyrroles        such as        4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,        cinnamamides such as        3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine,        and a variety of fungicides such as dodecylguanidine acetate,        3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,        hexachlorobenzene, methyl        N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,        DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)-alanine methyl        ester,        N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-amino-butyrolactone,        DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester,        5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,        3-[3,5-dichlorophenyl(5-methyl-5-methoxymethyl]-1,3-oxazolidine-2,4-dione,        3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,        N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,        2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,        1-[2-(2,4-dichloro-phenyl)pentyl]-1H-1,2,4-triazole,        2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,        N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,        1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole.

SYNTHESIS EXAMPLES

With due modification of the starting compounds, the protocol shown inthe synthesis example below was used for obtaining further compounds I.The resulting compounds I, together with physical data, are listed inthe Table I which follows. Further 5-chloro compounds of formula IIwhich were used for obtaining said further compounds I are listed infollowing Table II.

Example 1 Preparation of5-cyano-6-(2-chloro-6-fluorophenyl)-7-isopropylamino-[1,2,4]-triazolo[1,5-α]pyrimidine

A mixture of 0.1 mol5-chloro-6-(2-chloro-6-fluorophenyl)-7-isopropylamino-[1,2,4]-triazolo[1,5-α]pyrimidine[cf. EP-A 550 113] and 0.25 mol tetraethylammonium cyanide in 750 mldimethylformamde was stirred for about 16 hours at 20 to 25° C. To thismixture water and methyl-tert. butyl ether were added, the organic phasewas separated, washed with water, dried and filtered. Distillativeremoval of the solvent from the filtrate and chromatography over silicagel gave 7.1 g of the title compound of mp. 159° C.

Example 2 Preparation of5-methoxy-6-(2-chloro-6-fluorophenyl)-7-isopropylamino-[1,2,4]-triazolo[1,5-α]pyrimidine

To a solution of 65 mmol5-chloro-6-(2-chloro-6-fluorophenyl)-7-(4-methylpiperidin-1-yl)-[1,2,4]-triazolo[1,5-α]pyrimidine[cf. EP-A 550 113] in dry methanol 71.5 mmol of a 30% solution of sodiummethanolate were added at 20 to 25° C. After having stirred this mixturefor about 16 hours at this temperature methanol ws evaporated nad theresidue was dissolved with dichloromethane. The organic phase wasseparated, washed with water, dried and filtered. Distillative removalof the solvent from the filtrate and chromatography over silica gel gave4.2 g of the title compound of mp. 182° C.

TABLE I I

phys. data (m.p. [° C.], No. R¹ R² X IR [cm⁻¹]) I-1 CH₂C(CH₃)═CH₂ CH₂CH₃CN 139 I-2 CH(CH₃)₂ H CN 159 I-3 —(CH₂)₂CH(CH₃)(CH₂)₂— CN 196 I-4cyclopentyl H CN I-5 CH₂CH₃ CH₂CH₃ CN 212 I-6 CH₂CH₂CH₃ CH₂CH₂CH₃ CN I-7CH(CH₃)₂ CH₃ CN I-8 (±) CH(CH₃)—CH₂CH₃ H CN I-9 (S) CH(CH₃)—CH₂CH₃ H CNI-10 (R) CH(CH₃)—CH₂CH₃ H CN I-11 (±) CH(CH₃)—CH(CH₃)₂ H CN I-12 (S)CH(CH₃)—CH(CH₃)₂ H CN I-13 (R) CH(CH₃)—CH(CH₃)₂ H CN I-14 (±)CH(CH₃)—CH(CH₃)₃ H CN I-15 (S) CH(CH₃)—CH(CH₃)₃ H CN I-16 (R)CH(CH₃)—CH(CH₃)₃ H CN I-17 (±) CH(CH₃)—CF₃ H CN I-18 (S) CH(CH₃)—CF₃ HCN I-19 (R) CH(CH₃)—CF₃ H CN I-20 CH₂CF₃ H CN I-21 CH₂C(CH₃)═CH₂ CH₂CH₃OCH₃ I-22 CH(CH₃)₂ H OCH₃ I-23 —(CH₂)₂CH(CH₃)(CH₂)₂— OCH₃ 182 I-24cyclopentyl H OCH₃ I-25 CH₂CH₃ CH₂CH₃ OCH₃ I-26 CH₂CH₂CH₃ CH₂CH₂CH₃ OCH₃I-27 CH(CH₃)₂ CH₃ OCH₃ I-28 (±) CH(CH₃)—CH₂CH₃ H OCH₃ I-29 (S)CH(CH₃)—CH₂CH₃ H OCH₃ I-30 (R) CH(CH₃)—CH₂CH₃ H OCH₃ I-31 (±)CH(CH₃)—CH(CH₃)₂ H OCH₃ I-32 (S) CH(CH₃)—CH(CH₃)₂ H OCH₃ I-33 (R)CH(CH₃)—CH(CH₃)₂ H OCH₃ I-34 (±) CH(CH₃)—CH(CH₃)₃ H OCH₃ I-35 (S)CH(CH₃)—CH(CH₃)₃ H OCH₃ I-36 (R) CH(CH₃)—CH(CH₃)₃ H OCH₃ I-37 (±)CH(CH₃)—CF₃ H OCH₃ I-38 (S) CH(CH₃)—CF₃ H OCH₃ I-39 (R) CH(CH₃)—CF₃ HOCH₃ I-40 CH₂CF₃ H OCH₃ I-41 CH₂C(CH₃)═CH₂ CH₂CH₃ OCH₂CH₃ I-42 CH(CH₃)₂H OCH₂CH₃ I-43 —(CH₂)₂CH(CH₃)(CH₂)₂— OCH₂CH₃ 135 I-44 cyclopentyl HOCH₂CH₃ I-45 CH₂CH₃ CH₂CH₃ OCH₂CH₃ I-46 CH₂CH₂CH₃ CH₂CH₂CH₃ OCH₂CH₃ I-47CH(CH₃)₂ CH₃ OCH₂CH₃ I-48 (±) CH(CH₃)—CH₂CH₃ H OCH₂CH₃ I-49 (S)CH(CH₃)—CH₂CH₃ H OCH₂CH₃ I-50 (R) CH(CH₃)—CH₂CH₃ H OCH₂CH₃ I-51 (±)CH(CH₃)—CH(CH₃)₂ H OCH₂CH₃ I-52 (S) CH(CH₃)—CH(CH₃)₂ H OCH₂CH₃ I-53 (R)CH(CH₃)—CH(CH₃)₂ H OCH₂CH₃ I-54 (±) CH(CH₃)—CH(CH₃)₃ H OCH₂CH₃ I-55 (S)CH(CH₃)—CH(CH₃)₃ H OCH₂CH₃ I-56 (R) CH(CH₃)—CH(CH₃)₃ H OCH₂CH₃ I-57 (±)CH(CH₃)—CF₃ H OCH₂CH₃ I-58 (S) CH(CH₃)—CF₃ H OCH₂CH₃ I-59 (R)CH(CH₃)—CF₃ H OCH₂CH₃ I-60 CH₂CF₃ H OCH₂CH₃ I-61 CH₂C(CH₃)═CH₂ CH₂CH₃OCH(CH₃)₂ I-62 CH(CH₃)₂ H OCH(CH₃)₂ I-63 —(CH₂)₂CH(CH₃)(CH₂)₂— OCH(CH₃)₂156 I-64 cyclopentyl H OCH(CH₃)₂ I-65 CH₂CH₃ CH₂CH₃ OCH(CH₃)₂ 102 I-66CH₂CH₂CH₃ CH₂CH₂CH₃ OCH(CH₃)₂ I-67 CH(CH₃)₂ CH₃ OCH(CH₃)₂ I-68 (±)CH(CH₃)—CH₂CH₃ H OCH(CH₃)₂ I-69 (S) CH(CH₃)—CH₂CH₃ H OCH(CH₃)₂ I-70 (R)CH(CH₃)—CH₂CH₃ H OCH(CH₃)₂ I-71 (±) CH(CH₃)—CH(CH₃)₂ H OCH(CH₃)₂ I-72(S) CH(CH₃)—CH(CH₃)₂ H OCH(CH₃)₂ I-73 (R) CH(CH₃)—CH(CH₃)₂ H OCH(CH₃)₂I-74 (±) CH(CH₃)—CH(CH₃)₃ H OCH(CH₃)₂ I-75 (S) CH(CH₃)—CH(CH₃)₃ HOCH(CH₃)₂ I-76 (R) CH(CH₃)—CH(CH₃)₃ H OCH(CH₃)₂ I-77 (±) CH(CH₃)—CF₃ HOCH(CH₃)₂ I-78 (S) CH(CH₃)—CF₃ H OCH(CH₃)₂ I-79 (R) CH(CH₃)—CF₃ HOCH(CH₃)₂ I-80 CH₂CF₃ H OCH(CH₃)₂ I-81 CH₂C(CH₃)═CH₂ CH₂CH₃ OCH₂CH═CH₂I-82 CH(CH₃)₂ H OCH₂CH═CH₂ I-83 —(CH₂)₂CH(CH₃)(CH₂)₂— OCH₂CH═CH₂ 2990,1655, 985 I-84 cyclopentyl H OCH₂CH═CH₂ I-85 CH₂CH₃ CH₂CH₃ OCH₂CH═CH₂I-86 CH₂CH₂CH₃ CH₂CH₂CH₃ OCH₂CH═CH₂ I-87 CH(CH₃)₂ CH₃ OCH₂CH═CH₂ I-88(±) CH(CH₃)—CH₂CH₃ H OCH₂CH═CH₂ I-89 (S) CH(CH₃)—CH₂CH₃ H OCH₂CH═CH₂I-90 (R) CH(CH₃)—CH₂CH₃ H OCH₂CH═CH₂ I-91 (±) CH(CH₃)—CH(CH₃)₂ HOCH₂CH═CH₂ I-92 (S) CH(CH₃)—CH(CH₃)₂ H OCH₂CH═CH₂ I-93 (R)CH(CH₃)—CH(CH₃)₂ H OCH₂CH═CH₂ I-94 (±) CH(CH₃)—CH(CH₃)₃ H OCH₂CH═CH₂I-95 (S) CH(CH₃)—CH(CH₃)₃ H OCH₂CH═CH₂ I-96 (R) CH(CH₃)—CH(CH₃)₃ HOCH₂CH═CH₂ I-97 (±) CH(CH₃)—CF₃ H OCH₂CH═CH₂ I-98 (S) CH(CH₃)—CF₃ HOCH₂CH═CH₂ I-99 (R) CH(CH₃)—CF₃ H OCH₂CH═CH₂ I-100 CH₂CF₃ H OCH₂CH═CH₂I-101 CH₂C(CH₃)═CH₂ CH₂CH₃ OCHF₂ I-102 CH(CH₃)₂ H OCHF₂ I-103—(CH₂)₂CH(CH₃)(CH₂)₂— OCHF₂ 138 I-104 cyclopentyl H OCHF₂ I-105 CH₂CH₃CH₂CH₃ OCHF₂ I-106 CH₂CH₂CH₃ CH₂CH₂CH₃ OCHF₂ I-107 CH(CH₃)₂ CH₃ OCHF₂I-108 (±) CH(CH₃)—CH₂CH₃ H OCHF₂ I-109 (S) CH(CH₃)—CH₂CH₃ H OCHF₂ I-110(R) CH(CH₃)—CH₂CH₃ H OCHF₂ I-111 (±) CH(CH₃)—CH(CH₃)₂ H OCHF₂ I-112 (S)CH(CH₃)—CH(CH₃)₂ H OCHF₂ I-113 (R) CH(CH₃)—CH(CH₃)₂ H OCHF₂ I-114 (±)CH(CH₃)—CH(CH₃)₃ H OCHF₂ I-115 (S) CH(CH₃)—CH(CH₃)₃ H OCHF₂ I-116 (R)CH(CH₃)—CH(CH₃)₃ H OCHF₂ I-117 (±) CH(CH₃)—CF₃ H OCHF₂ I-118 (S)CH(CH₃)—CF₃ H OCHF₂ I-119 (R) CH(CH₃)—CF₃ H OCHF₂ I-120 CH₂CF₃ H OCHF₂

TABLE II II

phys. data No. R¹ R² (m.p. [° C.]) II-1 CH₂C(CH₃)═CH₂ CH₂CH₃ 136 II-2CH(CH₃)₂ H 143 II-3 —(CH₂)₂CH(CH₃) (CH₂)₂— 150 II-4 cyclopentyl H 62II-5 CH₂CH₃ CH₂CH₃ 167 II-6 CH₂CH₂CH₃ CH₂CH₂CH₃ 148 II-7 CH(CH₃)₂ CH₃151 II-8 (±) CH(CH₃)—CH₂CH₃ H 150 II-9 (S) CH(CH₃)—CH₂CH₃ H 147 II-10(R) CH(CH₃)—CH₂CH₃ H 147 II-11 (±) CH(CH₃)—CH(CH₃)₂ H 145 II-12 (S)CH(CH₃)—CH(CH₃)₂ H 145 II-13 (R) CH(CH₃)—CH(CH₃)₂ H 145 II-14 (±)CH(CH₃)—CH(CH₃)₂ H 188 II-15 (S) CH(CH₃)—CH(CH₃)₃ H 191 II-16 (R)CH(CH₃)—CH(CH₃)₃ H 191 II-17 (±) CH(CH₃)—CF₃ H 179 II-18 (S) CH(CH₃)—CF₃H 172 II-19 (R) CH(CH₃)—CF₃ H 172 II-20 CH₂CF₃ H 211 II-21 H H 250

Examples of the action against harmful fungi

The fungicidal action of the compounds of the formula I was demonstratedby the following experiments:

The active compounds, separately or together, were formulated as a 10%emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weightof Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying anddispersant action based on ethoxylated alkylphenols) and 10% by weightof Wettol® EM (nonionic emulsifier based on ethoxylated castor oil) anddiluted with water to the desired concentration.

Use Example 1: Action on Alternaria solani in Tomatoes

Leaves of pot grown tomato seedlings of the “Groβe Fleischtomate St.Pierre” variety were sprayed with aqueous liquors made from a stocksolution consisting of 10% of active ingredient, 63% of cyclohexanone,and 27% of emulsifier. After 24 hours the leaves were infected with azoospore suspension of Alternaria solani (1.7×10⁶ spores per ml of a 2%strength biomalt solution). The plants were then placed in a watervapour-saturated chamber. After 5 days the disease had spread to such agreat extent on the untreated plants that the fungicidal activity of thesubstances could be assessed.

In this test, the plants which had been treated with 63 ppm of compoundsI-1, I-3, and I-23 showed an infection of up to 3%, whereas theuntreated plants were infected to 100%.

Use Example 2: Action on Plasmopara viticola

Leaves of potted vines of the “Müller Thurgau” variety were sprayed withaqueous liquors made from a stock solution consisting of 10% of activeingredient, 63% of cyclohexanone, and 27% of emulsifier. To assess theduration of action, the plants were set up, after the sprayed-on layerhad dried, in the greenhouse for 8 days. Then the leaves were infectedwith a zoospore suspension of the fungus Plasmopara viticola, firstplaced in a vapour-saturated chamber at 24° C., and then kept for 5 daysin a greenhouse at 20 to 30° C. To accelerate and intensify thesporangiophore discharge, the plants were then again placed in the moistchamber for 16 hours. The extent of fungus attack was then assessed onthe undersides of the leaves.

In this test, the plants which had been treated with 250 ppm ofcompounds I-1 and I-2 showed an infection of up to 20%, whereas theuntreated plants were infected to 85%.

Active compounds A to E known from EP-A 550 113, WO-A 99/41255, and U.S.Pat. No. 5,994,360 resp., were used as comparison compounds in thefollowing comparison tests:

No. known from R X A EP-A 550 113, No. 106 isopropylamino chloro B EP-A550 113, No. 111 diethylamino chloro C WO-A 99/41255, No. 38 cyclohexylmethoxy D WO-A 99/41255, No. 39 cyclohexyl cyano E U.S. Pat. No.5,994,360, Ex. 1B 4-CH₃-piperidine methylComparison Test 1: Fungicidal Control of Early Blight on Tomatoes(Alternaria solani)

Young seedlings of tomato plants of the variety “Groβe Fleischtomate St.Pierre” were grown in pots to the 2 to 4 leaf stage. These plants weresprayed to run-off with an aqueous suspension, containing theconcentration of active ingredient mentioned in the table below,prepared from a stock solution containing 10% of the active ingredient,85% cyclohexanone and 5% emulsifier. The next day, the treated plantswere inoculated with an aqueous suspension of Alternaria solanicontaining 0.2×10⁶ spores per ml. Then the trial plants were immediatelytransferred to a humid chamber. After 6 days at 20 to 23° C. and arelative humidity close to 100%, the extent of fungal attack on theleaves was visually assessed as % diseased leaf area.

In this trial, the plants which have been treated with 250 ppm ofcompounds I-3 and I-23, resp., showed an infection of not more than 7%,whereas the plants treated with 250 ppm of comparison compounds C and D,resp., were infected to at least 60%, and the untreated plants wereinfected to 100%.

In another trial, the plants which have been treated with 16 ppm ofcompound I-3 showed an infection of 15%, whereas the plants treated with16 ppm of comparison compound E, were infected to 30%, and the untreatedplants were infected to 90%.

Comparison Test 2: Control of Net Blotch on Barley Caused by Pyrenophorateres

The first fully developed leaves of pot grown barley of the variety“Igri” were sprayed to run-off with an aqueous suspension, containingthe concentration of active ingredient or their mixture mentioned in thetable below, prepared from a stock solution containing 10% of the activeingredient, 85% cyclohexanone and 5% emulsifier. The next day thetreated plants were inoculated with an aqueous spore suspension ofPyrenophora teres tritici containing 0.02×10⁶ spores/ml. Then the trialplants were immediately transferred to a humid chamber in thegreenhouse. After 6 days of cultivation at 20 to 24° C. and a relativehumidity close to 100%, the extent of fungal attack on the leaves wasvisually assessed as % diseased leaf area.

In this trial, the plants which have been treated with 250 ppm ofcompounds I-3 and I-23, resp., showed an infection of not more than 7%,whereas the plants treated with 250 ppm of comparison compounds C and D,resp., and the untreated plants were infected to 100%.

Comparison Trial 3: Fungicidal Control of Leaf Blotch on Wheat Caused bySeptoria tritici (Protective)

Leaves of pot-grown wheat seedling of the variety “Riband” were sprayedto run-off with an aqueous suspension, containing the concentration ofactive ingredient as described below prepared from a stock solutioncontaining 10% of the active ingredient, 85% cyclohexanone and 5%emulsifier. The plants were allowed to air-dry. At the following day theplants were inoculated with an aqueous spore suspension of Septoriatritici containing 2.0×10⁶ spores/ml. Then the trial plants wereimmediately transferred to a humid chamber. After 2 weeks at 18 to 22°C. and a relative humidity close to 100% the extent of fungal attack onthe leaves was visually assessed as % diseased leaf area.

In this trial, the plants which have been treated with 63 ppm ofcompounds I-3, I-5 and I-23, resp., showed no infection, whereas theplants treated with 63 ppm of comparison compounds B, C and D, resp.,were infected from 20 to 60%, and the untreated plants were infected to90%.

Comparison Test 4: Fungicidal Control of Rice Blast Caused byPyricularia oryzae (Protective)

Leaves of pot-grown rice seedling of the variety “Tai-Nong 67” weresprayed to run-off with an aqueous suspension, containing theconcentration of active ingredient as described below prepared from astock solution containing 10% of the active ingredient, 85%cyclohexanone and 5% emulsifier. The plants were allowed to air-dry. Atthe following day the plants were inoculated with an aqueous sporesuspension of Pyricularia oryzae containing 1.0×10⁶ spores/ml. Then thetrial plants were immediately transferred to a humid chamber. After 6days at 22 to 24° C. and a relative humidity close to 100% the extent offungal attack on the leaves was visually assessed as % diseased leafarea.

In this trial, the plants which have been treated with 250 ppm ofcompounds I-3, I-5, I-23, and I-63 resp., showed an infection of up to30%, whereas the plants treated with 250 ppm of comparison compounds A,B, and E, resp., were infected from 60 to 80%, and the untreated plantswere infected to 90 to 100%.

Comparison Test 5: Protective Control of Powdery Mildew on Cucumber

Cucumber seedlings of the variety “Chinesische Schlange” were grown inpots to the 2 leaf stage. The plants were then sprayed to run-off withan aqueous suspension, containing the concentration of active ingredientas described below, prepared from a stock solution containing 10% of theactive ingredient, 85% cyclohexanone and 5% emulsifier. The next day thetreated plants were inoculated with an aqueous spore suspension ofcucumber powdery mildew (Sphaerotheca fuliginea). Then the trial plantswere cultivated in a greenhouse at temperatures between 20 and 24° C.and a relative humidity between 60 and 80.%. After 8 days the extent offungal attack on the leaves was visually assessed as % diseased leafarea.

In this trial, the plants which have been treated with 16 ppm ofcompound I-23 showed no infection, whereas the plants treated with 16ppm of comparison compound E were infected to 90%, and the untreatedplants were infected to 100%.

1. 6-(2-Chloro-6-fluoro-phenyl)-triazolopyrimidines of formula I

in which R¹ is straight-chain or branched C₁–C₁₀-alkyl,C₃–C₈-cycloalkyl, C₅–C₉-bicycloalkyl, C₃–C₈-cycloalkyl-C₁–C₆-alkyl,C₁–C₁₀-alkoxy-C₁–C₆-alkyl, C₁–C₁₀-haloalkyl, or is a phenyl group whichis optionally substituted by one to three halogen atoms or C₁–C₁₀-alkylor C₁–C₁₀-alkoxy groups, R² is hydrogen, C₁–C₁₀-alkyl orC₁–C₁₀-haloalkyl, and X is cyano, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy orC₃–C₈-alkenyloxy.
 2. Compounds of formula I according to claim 1 inwhich R¹ is branched C₃–C₁₀-alkyl, C₃–C₈-cycloalkyl, C₅–C₉-bicycloalkyl,C₃–C₈-cycloalkyl-C₁–C₆-alkyl, C₁–C₁₀-alkoxy-C₁–C₆-alkyl,C₁–C₁₀-haloalkyl, or is a phenyl group which is optionally substitutedby one to three halogen atoms or C₁–C₁₀-alkyl or C₁–C₁₀-alkoxy groups,R² is hydrogen, C₁–C₁₀-alkyl or C₁–C₁₀-haloalkyl, and X is cyano,C₁–C₆-alkoxy, C₁–C₆-haloalkoxy or C₃–C₈-alkenyloxy.
 3. Compounds offormula I according to claim 2 in which R¹ is branched C₃–C₆-alkyl,C₁–C₆-haloalkyl, C₃–C₆-cycloalkyl, or C₅–C₉-bicycloalkyl, and R² ishydrogen or C₁–C₆-alkyl.
 4. Compounds according to claim 2 in which R²is hydrogen.
 5. Compounds according to claim 2 in which X is methoxy. 6.Compounds according to claim 2 in which X is cyano.
 7. Compounds offormula I according to claim 1, in which R¹ is straight chained orbranched C₁–C₆-alkyl, C₁–C₆-haloalkyl, C₃–C₆-cycloalkyl, orC₅–C₉-bicycloalkyl, and R² is hydrogen or C₁–C₆-alkyl.
 8. Compoundsaccording to claim 1 in which R² is hydrogen.
 9. Compounds according toclaim 1 in which X is methoxy.
 10. Compounds according to claim 1 inwhich X is cyano.
 11. A composition suitable for controllingphytopathogenic fungi, comprising a solid or liquid carrier and acompound of the formula I as claimed in claim
 1. 12. A method forcontrolling phytopathogenic fungi, which comprises treating the fungi orthe materials, plants, the soil or the seed to be protected againstfungal attack with an effective amount of a compound of the formula I asclaimed in claim
 1. 13. A process for the preparation of compounds offormula I as defined in claim 1 which comprises reacting5-halogen-6-phenyl-triazolopyrimidines of formula II

in which Y is halogen with a compound of formula IIIM-X  III in which M is an ammonium-, tetraalkylammonium-, alkali metal-or alkaline earth metal cation and X is as defined in formula I toproduce compounds of formula I.